ES2429814T3 - Modified polyamide molding mass for impact resistance as well as container formed from it - Google Patents

Abstract

Molding mass of thermoplastic polyamide, which contains a) from 71 to 89% by weight of an MXD6 / MXDI copolyamide, being the molar part of isophthalic acid, with respect to all diacids isophthalic acid and adipic acid, from 1 to 30 mol%, b) from 11 to 29% by weight of at least one acid-modified copolyolefin elastomer or at least one acid-modified combination of several copolyolefin elastomers, c) from 0 to 8% by weight of additives, not containing, in addition to copolymers a) and b), other polymers and / or copolymers and adding components a) to c) to 100% by weight.

Description

Modified polyamide molding mass for impact resistance as well as container formed from it

The present invention relates to an impact modified polyamide molding mass that is particularly suitable for the production of containers with a good oxygen barrier and cold impact resistance. In addition, the present invention relates to containers that are produced from the molding mass of thermoplastic polyamide. Particularly, from the polyamide molding mass according to the invention, storage or transport containers can be produced for industrial chemicals, agrochemicals, the cosmetic industry, pharmaceutical industry or food industry.

Modified polyamide molding masses that are suitable for container production are already known to the state of the art. Thus, EP 1 752 492 refers to a thermoplastic fuel barrier resin composition which, in addition to a polyamide, a modified polyolefin or a styrene copolymer is essentially composed of a polyolefin.

EP 1 942 296 discloses a multilayer hydraulic line with a layer of a combination of polyamide 610 as the main component, an amorphous or microcrystalline polyamide based on MXDA or PXDA and an impact modifier.

The high content of polyolefins or polyamide 610 in such resin compositions, however, causes a reduced oxygen barrier and also has an effect, in the case of polyolefin, disadvantageous on the impact resistance of notched specimen and the result of Gelboflex resins tests.

In this regard, it is an object of the present invention to provide a polyamide composition that exhibits excellent oxygen barrier properties and that possesses good mechanical properties.

This objective is achieved, with respect to the molding mass, with the characteristics of claim 1. In addition, according to the invention a container is indicated whose characteristics are reproduced in claim 9. Possibility of use is indicated with claim 14 of the containers according to the invention.

According to the invention, therefore, a thermoplastic polyamide molding mass is provided which

a) contains from 71 to 89% by weight of an MXD6 / MXDI copolyamide, the molar part being isophthalic acid, with respect to all the diacids isophthalic acid and adipic acid, from 1 to 30 mol%,

b) from 11 to 29% by weight of at least one acid modified copolyol olefin elastomer or at least one acid modified combination of several copolyol olefin elastomers as well as

c) from 0 to 8% by weight of additives,

not containing, in addition to copolymers a) and b), other polymers and / or copolymers and adding components a) to c) to 100% by weight.

The polyamide molding mass according to the invention, therefore, is essentially composed of an MXD6 / MXDI copolyamide matrix, into which an acid-modified copolylolefin elastomer or a combination of several copolylolefin elastomers is introduced by preparation. By the additives, according to the invention, no other polymers are understood.

In the case of the polyamide molding mass according to the invention it is an impact modified polyamide molding mass for the production of cold impact resistant containers with an excellent oxygen barrier.

Surprisingly, it was shown that the polyamide molding mass according to the invention has a reduced water vapor permeability and a great solvent barrier, for example, against Nmethylpyrrolidone, dimethylsulfoxide or xylene.

In addition, surprisingly it was found that the barrier material, despite the modification with the copolyolefin elastomer, which itself has a bad oxygen barrier, retains practically unchanged its barrier effect and that, in addition, the containers produced from from this they resist the drop test from at least 1.8 m in height, that is, they also show excellent mechanical stability.

For the preparation of the polyamide molding dough, the modified copolyolefin elastomer is mixed with the copolyamide to a dry combination. This dry combination can be extruded for subsequent homogenization and then processed or processed directly. Preferably, the dry combination is extruded first and then processed.

By the acid-modified combination of several copolylolefin elastomers, a mixture of the ethylene-propylene copolymer, ethylene-but-1-ene copolymer, propylene-but-1-yne copolymer, polyethylene and / or polypropylene copolymer is to be understood. The mixture is homogenized in the melt, in this respect the acid modification is also carried out by grafting, so that the degree of modification is from 0.3 to 1.5% by weight, preferably from 0.4 to 1 , 2% by weight, particularly preferably 0.4 to 1.0% by weight, with respect to the mixture.

If the mixture of the copolyolefin elastomers is used as a dry combination, that is, without homogenization in the melt, then at least a part of the components has already been modified with acid, for example, in such a range that the degree of modification of the entire dry combination is 0.3 to 1.5% by weight, preferably 0.4 to 1.2% by weight, particularly preferably 0.4 to 1.0% by weight. Eventually, such a dry combination can also be further homogenized in the melt.

The selection of the polyamide molding mass is carried out, due to the oxygen barrier (especially with high air humidity), the Gelboflex value and the impact on a fitted specimen (especially at low temperature). The elongation at breakage is also considered as a criterion for resistance. In this way, the molding mass according to the invention can be optimally adapted or adjusted to the existing external conditions or to the theoretical requirements.

In a preferred embodiment, 0.2 to 4% by weight of additives can be added to the polyamide composition. In this regard, more preferably the amount of each individual additive amounts to a maximum of 3% by weight.

The additive is preferably selected from the group consisting of inorganic stabilizers, organic stabilizers, lubricants, colorants and markers, inorganic pigments, organic pigments, antistatics, conductivity additives, soot, graphite, carbon nanotubes, optical illuminators, low weight compatibility mediators molecular, particle-shaped fillers, particularly nanoscale fillers such as, for example, minerals with a particle size of at most 100 nm or natural or synthetic, unmodified phyllosilicates

or modified, or mixtures thereof.

As stabilizers or anti-aging agents, they can be used in the polyamide compositions according to the invention, for example antioxidants, antioxidants, photoprotectors, UV stabilizers, UV absorbers or UV blockers.

The particulate fillers are preferably selected from the group consisting of minerals, talc, mica, dolomite, silicates, quartz, titanium dioxide, wollastonite, kaolin, silicic acids, magnesium carbonate, magnesium hydroxide, crete, ground glass, flakes of glass, ground carbon fibers, ground or precipitated calcium carbonate, lime, feldspar, barium sulfate, glass balls, hollow glass balls, hollow ball silicate fillers, synthetic stratified silicates, natural stratified silicates and mixtures of same.

Loads in the form of particles may be treated on the surface. This can occur with a suitable finishing or adherent system. For this, systems based on fatty acids, waxes, silanes, titanates, polyamides, urethanes, polyhydroxyethers, epoxides, nickel or combinations or mixtures thereof can be used, for example.

As phyllosilicates they can be used in the polyamide compositions according to the invention, for example, kaolins, serpentines, talc, mica, vermiculite, muscovite, illite, smectite, saponite, montmorillonite, hectorite, double hydroxides or mixtures thereof. Stratified silicates may be surface treated (modified), however, also untreated (unmodified).

As antistatic and / or conductivity additives they can be used in the polyamide compositions according to the invention, for example, soot and / or carbon nanotubes, also called carbon nanofibrils.

The use of soot can be used, for example, for the black coloring of polyamide compositions.

A preferred embodiment of the molding mass of thermoplastic polyamide provides that the molar part of isophthalic acid in the MXD6 / MXDI copolyamide, with respect to all diacids isophthalic acid and adipic acid, is 1 to 20 mol% , preferably 2 to 15 mol%, particularly preferably 2 to 12 mol%. In addition, it is preferred that the at least one acid-modified copolylolefin elastomer or the at least one acid-modified combination of several copolyolphine elastomers is composed of monomer units that are selected from the group consisting of ethylene d), propylene e) and but -1-ene f), preferably using the monomers mentioned above in the following molar parts:

d) ethylene: 65-90 mol%, preferably 65-87 mol%, particularly preferably 71-84 mol%,

e) propylene: 8-33 mol%, preferably 10-25 mol%, particularly preferably 12-20 mol% as well as

f) but-1-ene: 2-25 mol%, preferably 3-20 mol%, particularly preferably 4-15 mol%, very particularly preferably 4-9 mol% and adding the components d ) af) up to 100 mol%.

According to this embodiment, therefore, it may be provided that the copolyolefin elastomer contains the d) af) monomers mentioned in the indicated preferred molar parts, however, it is also possible to mix several copolylolefin elastomers containing, respectively, two of the monomers d) af), that is, d) and e), d) and f) or e) and f), such that monomers d) to f) are present in the mixture in the molar parts preferred. Particularly preferably, the mixture is composed of a copoly-olefin elastomer of monomers d) and e) and a copoly-olefin elastomer of monomers d) and f), such that monomers d) to f) are present in the mixture. the preferred molar parts.

Furthermore, it is advantageous that the acid modification of the copolylophine elastomer or of the combination of several copolyolphine elastomers is carried out by grafting with unsaturated carboxylic acids and / or derivatives of unsaturated carboxylic acids, preferably a carboxylic acid derivative selected from the group consisting of esters of unsaturated carboxylic acids and anhydrides of unsaturated carboxylic acids, particularly with an unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, alphaethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic acid, tetrahydrophthalic acid and / or butenylsuccinic acid, that is, that the copolylophine elastomer contains unsaturated carboxylic acids and / or derivatives of grafted unsaturated carboxylic acids in the molecule. The conditions under which the graft of the copolyolefin elastomer develops are sufficiently known to the expert.

In this respect, the advantageous degrees of modification, that is, the parts by weight of the unsaturated carboxylic acids and / or the derivatives of unsaturated carboxylic acids in the copolylolefin elastomer or in the combination of various copolylolefin elastomers are found in 0.3 to 1.5% by weight, preferably 0.4 to 1.2% by weight, particularly preferably 0.4 to 1.0% by weight.

A particularly preferred embodiment of the invention provides that the relative viscosity of MXD6 / MSDI copolyamide, measured in a 0.5% m-cresol solution by weight at 20 ° C, is 1.40 to 1.80, preferably from 1.46 to 1.73, particularly preferably from 1.51 to 1.69, very particularly preferably from 1.53 to 1.66.

Preferably, the MXD6 / MSDI copolyamide has a maximum of 70 mequiv / kg, particularly preferably 5 to 50 mequiv / kg, very particularly preferably 10 to 29 mequiv / kg of amino terminal groups. Preferably, a MXD6 / MSDI copolyamide is combined with 5 to 50 mequiv / kg of amino terminal groups with copolyolefin elastomers or a combination of several copolylolefin elastomers with a degree of modification of 0.4 to 1.2% by weight.

Particularly preferably, an MXD6 / MSDI copolyamide is combined with 10 to 29 mequiv / kg of amino terminal groups with copolyolefin elastomers or a combination of several copolylolefin elastomers with a degree of modification of 0.4 to 1.0% by weight .

Particularly good mechanical properties can be achieved when

a) the part by weight of the copolyamide in the polyamide molding mass is 73 to 87% by weight, preferably 75 to 85% by weight, particularly preferably from 77 to 83 and / or

b) the part by weight of the at least one acid-modified copoly-olefin elastomer in the polyamide molding mass or of the at least one acid-modified combination of several copolylolefin elastomers in the polyamide molding mass is from 13 to 27 % by weight, preferably 15 to 25% by weight, particularly preferably 17 to 23% by weight.

The polyamide molding mass according to the invention is particularly characterized in that, apart from copolymers a) and b), no other polymers and / or copolymers are contained.

The polyamide molding mass according to the invention is not transparent.

In an alternative embodiment, the polyamide molding mass according to the invention is composed of the constituents a) to c), not being understood by c) according to the invention other polymers.

For the preparation of the polyamide molding dough according to the invention, components a) and b), optionally components a) to c), are mixed in the molten state. This occurs in usual preparation machines such as, for example, single or twin screw extruders or screw kneaders. In this regard, the components are dosed individually at the inlet or supplied in the form of a dry combination.

For the preparation of the dry combination, the dried granules and possibly other additives (additional substances) are mixed. This mixture is homogenized by an asymmetric movement mixer, eccentric wheel mixer or asymmetric movement dryer for 10 to 40 minutes. To prevent moisture absorption, this can be done with a dried protective gas.

The preparation is carried out with adjusted cylinder temperatures of 220 to 300 ° C and an adjusted temperature of the inlet zone of 70 to 120 ° C. A vacuum can be applied in front of the nozzle or atmospheric degassing. The melt is discharged in an extruded form, cooled in a water bath at 10 to 80 ° C and then granulated. The granulate is dried for 10 to 24 hours at 80 to 120 ° C with nitrogen or under vacuum to a water content below 0.1% by weight, preferably below 0.05% by weight.

According to the invention, an opaque multilayer container is also provided, in which at least one layer is produced from a molding mass according to the invention, described above. In the case of this layer it can be an intermediate layer or the internal layer. Several layers of polyamide molding dough may also be contained in the container. Preferably, the polyamide molding layer forms the innermost layer of the container, that is, the layer that directly delimits the internal space of the container. Therefore, the inner layer is in direct contact with the filler product. The preferred type of this container, therefore, is for example a tank, barrel, drum, bottle or tube or the like. Preferably they are rigid containers. With respect to its geometric dimensions, the container is not limited, so that "containers" according to the invention are included in the term, for example, drums, tanks or similar containers that can be closed, however, also tubes.

Preferably, the container has three to seven layers.

Preferably, the container has at least one layer of a polyolefin.

The term polyolefin comprises, in this context, in addition to homopolyolefins, also copolyolefins, grafted polyolefins, grafted copolyolefins, ionomers and copolymers of olefins with acrylic acid, derivatives of acrylic acid (for example, methacrylic acid, acrylonitrile, methyl ester of methacrylic acid, butyl methacrylic acid, glycidyl methacrylate), vinyl acetate, maleic acid anhydride, other olefins and / or styrene.

The preferred layer thicknesses of the at least one layer of the container, which is produced from the molding mass according to the invention, in this regard are 15 to 800 µm, preferably 20 to 500 µm, of particularly preferably from 25 to 250 µm, very particularly preferably from 30 to 150 µm.

Thanks to the use of the molding mass according to the invention for the production of at least one layer of the container, surprisingly, at the same time, good mechanical properties can be granted to the container as well as a very good oxygen barrier.

In this regard, the preferred wall thicknesses of the container, that is, all of the layers of which the container is formed are 500 µm to 10 mm, preferably 600 µm to 6 mm, particularly preferably 700 ! to 3 mm.

With respect to the containers according to the invention, there is no particular preferred limit for the capacity, however, the advantageous effects discussed above are particularly evident with a capacity of 0.5 to 220 l, preferably from 0.5 to 80 l, more preferably from 0.75 to 20 l, particularly preferably from 1 to 5 l.

In containers with a volume of 1 to 5 l, the wall thickness is preferably 700 µm to 2.5 mm, particularly preferably 900 µm to 1.8 mm. The layer thickness of the at least one layer that is produced from the molding mass according to the invention, in these containers, is preferably 25 µm to 250 µm, particularly preferably 35 µm to 120 µm. m.

In the case of containers with a volume of 80 to 220 l, the wall thickness is preferably 2.5 mm to 10 mm, particularly preferably 2.5 mm to 6 mm. The layer thickness of the at least one layer that is produced from the molding mass according to the invention, in these containers, preferably is from 80 µm to 800 µm, particularly preferably from 80 µm to 400! m.

The wall thickness, that is, all of all the layers from which the container is formed and the layer thickness of the at least one layer that is produced from the molding composition according to the invention, is measured in a cut through the container at medium height and, in fact, at four points that are 90 degrees apart from each other respectively. In the case of angled containers, these four points are preferably located in the center of the lateral surfaces. The wall thickness can be determined at these points directly or by a microtome cut. The layer thickness of the at least one layer that is produced from the molding mass according to the invention is determined by a microtome cut. The measurement is carried out in three containers. In the case of the indicated values, it is the arithmetic mean of these 12 measurement values.

Examples of the layer structure of a container are: 3-layer container:

PO / HV / PA Regranulated PO + / HV / PA

4 layer container:

PO / regranulated / HV / PA PO / PO + regranulate / HV / PA

5 layer container:

PO / regranulated / PO / HV / PA PO / HV / PA / HV / PO

6 layer container:

PO / regranulated / HV / PA / HV / PO PO / regranulated / HV / PA / HV / PO

7 layer container:

PO / HV / PA / HV / PO / HV / PA PO / PO + regranulated / HV / PA / HV / PO + regranulated / PO PO / regranulated / HV / PA / HV / regranulated / PO PO polyolefin Adherent hv PA polyamide molding mass according to the invention

A bonding layer is preferably always used between a polyolefin layer and a polyamide layer. Adhesives or adherent concentrates available in the market serve as adherent in this regard. In the case of containers of up to 20 l, the adherent can also be introduced by mixing into the polyolefin layer, then its part in this layer is 10 to 50% by weight, preferably 15 to 25% by weight.

Each polyolefin layer that is outside or included may contain regranulate and, in fact, up to 70% by weight, preferably up to 50% by weight, particularly preferably up to 40% by weight. In this respect, by regranulation, the remains of the material that are produced during the production of the container, such as, for example, starting material, slices or spoiled containers, which are crushed before the addition are to be understood. The regranulate can also be used as its own layer.

The containers according to the invention are characterized by extremely high mechanical stability, which will be explained by a test experiment. For this, the container according to the invention is filled with a mixture of ethylene glycol-water in a volume ratio of 1: 2 and stored for 24 hours at 48 hours at -20 ° C. The containers according to the invention, which are filled with such a mixture of solvent and tempered, however, surprisingly do not break with a drop from 1.8 m, preferably from 2.0 m, particularly preferably from 2.2 m

Purposes of using the containers according to the invention are, in particular, the production of containers for agrochemicals (for example, herbicides, pesticides, fungicides, fertilizers), industrial chemicals, industrial precursor and intermediate products, precursor products or cosmetic items (for example, solvent, flavor solutions, mascara, nail polish), precursor products or pharmaceutical articles and / or precursor products for the food industry (for example, saporifers, additives).

In the case of agrochemicals, these are containers for the final consumer. In the case of industrial chemicals, containers for the final consumer and the business to business environment. In the other uses, of containers for the field of business to business.

The preferred application of the polyamide molding masses according to the invention are containers (EBM or ISBM containers) produced by extrusion and blow molding or blow and distension projection molding with a volume of 0.5 l to 220 l. In this regard, the polyamide molding layer can be used as an intermediate or internal layer. Several layers of polyamide molding dough may also be contained.

Vessels with a volume of 0.5 l to 20 l are produced by extrusion and blow molding or blow and distension projection molding. Larger containers are preferably manufactured by extrusion and blow molding.

The processability to give flat sheets and their properties are very relevant for the application of the polyamide molding masses according to the invention, since the at least one layer of the polyamide molding mass according to the invention in the container , depending on the size of the container, it can only reach a sheet thickness.

The advantageous properties associated with the molding mass according to the invention are further clarified by the following examples, without limiting the invention thereto. The compounds used in Tables 2 to 6 are indicated in the following Table 1.

The water vapor permeability of the polyamide molding mass according to the invention of Examples 1, 2 and 4 amounts (measured on flat sheets of thickness 50 µm to 23 ° C and 85% relative humidity) to:

Example 1 6.5 g / m2 d Example 2 6.4 g / m2 d Example 4 6.7 g / m2 d

The following measurement specifications are used to examine polyamide molding masses.

Relative viscosity

10 ISO 307 0.5% m-cresol solution by weight

or for PA 6 1.0% solution by weight in 96% sulfuric acid 20 ° C temperature Relative viscosity (VR) calculation according to VR = t / t0 based on section 11 of the standard.

15 Melting Point

ISO 11357-1 / -2 Granulated Differential scanning calorimetry (DSC) was carried out with a heating rate of 20 K / min. The melting point indicated the temperature at the peak maximum.

20 Determination of amino terminal groups

To determine the amino terminal groups, the polyamide is dissolved in hot m-cresol and mixed with isopropanol. The content of amino terminal groups is established by potentiometric titration with perchloric acid.

Tensile elasticity modulus:

25 ISO 527 with a tensile speed of 1 mm / min ISO tensile test bar, standard: ISO / CD 3167, Type A1, 170 x 20/10 x 4 mm, temperature 23 ° C

Elongation at break:

ISO 527 with a tensile speed of 50 mm / min 30 Bar for ISO tensile tests, standard: ISO / CD 3167, Type A1, 170 x 20/10 x 4 mm, temperature 23 ° C

Impact resistance according to Charpy:

ISO 179 / * eU ISO test bar, standard: ISO / CD 3167, type B1, 80 x 10 x 4 mm, temperature 23 ° C or -30 ° C 35 * 1 = not instrumented, 2 = instrumented

Impact resistance of notched specimen according to Charpy:

ISO 179 / * eA ISO test bar, standard: ISO / CD 3167, type B1, 80 x 10 x 4 mm, temperature 23 ° C or -30 ° C * 1 = not instrumented, 2 = instrumented

40 Oxygen barrier measurement

ASTM D 3985-5 Flat sheet, thickness 50 µm Temperature and relative humidity corresponding to the indication in the tables Mocon OX-Tran 2/20 measuring device from Mocon. The calibration of the measuring device is

45 carried out with a "Juliett" polyester calibration sheet 0.95 thousand (24.13 µm) thick from Mocon.

The measurement is performed in the carrier gas procedure.

Determination of water vapor permeability

DIN 53122-1

Flat sheet, thickness 50 µm, diameter approximately 90 cm examination climate 23 ° C, 85% relative humidity. An aluminum dish that is loaded with approximately 150 g of silica gel as an absorbent is closed by the sample by means of a threaded fastening ring and inserted into the desiccator. The volume of water vapor that passes through the test area of the sample surface and that is absorbed by the absorbent is determined from the increase in mass of the heavy dish every 24 hours. The increase in mass is followed over 28 days.

Gelboflex test

ASTM F 392 Flat sheet, DIN A4, thickness 50 µm Stroke 155 mm 440 ° torsion angle Speed 45 cycles / min Temperature 23 ° C

Gelbo Flex Tester Model G0002 measuring device from IDM Instruments. The measurement is performed at 900 cycles. For the counting of the holes produced in the sheet the flexed sheet is placed on a filter paper and both are fixed with a frame on a perforated plate. The perforated plate is exposed to a water jet vacuum and then distributed on the ink sheet with a sponge or a brush. The holes become visible as colored marks on the filter paper and can be counted. The quantity of the holes is indicated per m2. The value indicated in the tables represents the arithmetic mean value of 5 measurements.

Drop test

ADR / RDI 2009 Section 6.1 3-layer bottle with the following layer thicknesses from outside to inside 1350/40/65! M and a volume of 1 l of water / ethylene glycol filler product 2/1 Temperature -20 ° C Bottles (10 pieces per drop height) are stored from 24 to 48 h at -18 ° C and checked directly after extraction. To withstand the drop height, the 10 bottles have to be still tight after the test.

Determination of the solvent barrier

3-layer bottle with the following layer thicknesses from the outside inwards 1350/40/65 µm and a volume of 1 l of N-methylpyrrolidone filler product Temperature 40 ° C Storage duration 60 days

Storage is carried out in a drying oven for circulating air in a well ventilated space. 5 bottles are examined respectively. Weight loss is determined after 30, 40, 50 and 60 days.

The specimens for tensile and impact tests were produced in an injection molding machine of the Arburg company, model Allrounder 420 C 1000-250. In this regard, rising cylinder temperatures of 265 ° C to 285 ° C were used. The molding temperature was 80 ° C. The specimens were used in the dry state, for this they were stored after injection molding for at least 48 h at room temperature in a dry environment, that is, on silica gel.

The production of the flat sheet (thickness 50 µm) was carried out in a Collin flat sheet installation with a 3-zone worm (diameter 30 mm) at cylinder temperatures of 240 to 260 ° C and a head temperature and nozzle respectively 260 ° C. The temperature of the cooling cylinder amounted to 15 ° C with a tool width of 300 mm and a tool outlet groove dimension of 0.7 mm. The 50 µm flat sheets are translucent.

The production of the 3-layer bottles was carried out in a Bekum double station blowing installation with three extruders. In the extruder, cylinder temperatures of 245/255/255 ° C and a nozzle temperature of 245 ° C were adjusted for the polyamide molding mass according to the invention. For the processing of impact modified PA 6, cylinder temperatures of 245/245/245 ° C and a nozzle temperature of 235 ° C were used. The other extruders were operated correspondingly to the recommendations of the material manufacturers. The molding temperature was 20 ° C. The weight of the bottle amounted to 105 g.

Bottle layer structure:

outer layer / HV / inner layer

with the following layer thicknesses 1350/40/65 µm.

As the outer layer a mixture of HDPE (65% by weight) and a regranulate (35% by weight) or HDPE alone (100% by weight) was used.

The polyamide molding mass according to the invention of Example No. 2, an impact modified polyamide 6 or EVOH was used as the inner layer.

HDPE: Sabic HD58 type B5823

(MFI 23 at 190 ° C and 21.6 kg)

HV: Mitsui Admer NF 408 E Type

(MFI 1.6 at 190 ° C and 2.16 kg)

PA6, modified to impact:

80% by weight of PA 6 (VR 2.75, in sulfuric acid) 20% by weight Tafmer MC 201 (oxygen permeability at 23 ° C: 50% RH 50 cm3 / m2 d bar 85% RH 80 cm3 / m2 d bar water vapor permeability at 23 ° C, 85% RH: 13 g / m 2 d)

EVOH: Kuraray Type EVAL F 101 B

(32 mol% PE, MFI 1.6 at 190 ° C and 2.16 kg)

Preparation example for polyamide compositions

The preparation of a PA molding mass according to the invention is explained below by the molding mass of Example No. 2, the other examples and comparative examples were prepared analogously:

The molding dough was prepared in a twin-screw extruder from Werner & Pfleiderer Type ZSK 25. For the preparation of the dry combination, the dried granules (copolyamide and copolylolefin) were mixed. This mixture is homogenized for 30 minutes by an asymmetric mixer. The dry combination was dosed by a scale at the entrance.

The temperature of the first cylinder was set at 100 ° C, that of the remaining cylinders ascending from 230 to 300 ° C. A rotation speed of 300 rpm and a yield of 15 kg / h was used and atmospheric degassed. The bars were cooled in the water bath, cut and the granulate obtained was dried at 120 ° C for 24 h to a water content below 0.1% by weight.

Tables 2 and 3 show examples according to the invention, component b) being mixed according to Table 3 from two olefin copolymers.

Tables 4 to 6 contain comparative examples. Table 4 shows comparative examples with a too small or too high part of component b). Tables 5 and 6 have been prepared according to the state of the art mentioned at the beginning.

Table 7 summarizes the results of the drop test and the determination of the solvent barrier.

In the case of Examples 1 to 11, these are examples according to the invention with polyamide molding masses of an MXD6 / MXDI copolyamide and an acid modified copolylolefin elastomer (Table 2) or an acid modified combination of several copolyolefin elastomers (Table 3). They show low oxygen permeabilities with, at the same time, reduced tendency to hole formation in the Gelboflex test. Also the impact resistance of notched specimen are high.

Comparative Examples 12 and 13 show that 10% by weight of the acid-modified copoly-olefin elastomer (B1) in the MXD6 / MXDI PA is not yet sufficient, since the sheet produced from this is destroyed in the Gelboflex test. . In addition, only reduced impact resistance of the fitted specimen is obtained. On the other hand, 30% by weight of the acid modified copolyolphine elastomer (B1) in the MXD6 / MXDI PA are too much (Comparative Example 14), since the molding mass then has so many gel particles that it cannot be produce a sheet

Tables 5 and 6 (Comparative Examples 15 and 19) show other results obtained in polyamide molding masses not according to the invention. In this regard, the polyamide molding masses of Table 5 are made according to EP 1 752 492 A1 and those of Table 6, according to EP 1 942 296 A1.

The molding masses prepared in Comparative Examples 15 and 16 according to EP 1 752 492 A1 have too many gel particles, such that a sheet can no longer be produced (Comparative Example 15) or has too high oxygen permeability and a resistance that is too low (Comparative Example 16).

5 The molding masses prepared in Comparative Examples 17 to 19 according to EP 1 942 296 A1 in their entirety have too high oxygen permeabilities.

Table 7 shows the results of the fall tests with 3-layer bottles filled and refrigerated. Bottles with the inner layer of the molding mass according to the invention of Example No. 2 resist a fall from a height of 2.20 m and, therefore, show the best result of all the bottles

10 rehearsed

Bottles with impact modified polyamide 6 as an inner layer certainly resist a drop from 1.80 m in height, however, impact modified polyamide 6 has considerably greater oxygen permeability than molding masses according to the invention. .

In addition, bottles with impact modified polyamide 6 as an inner layer show a worse barrier against

N-methylpyrrolidone than the bottles with the molding mass according to the invention of Example No. 2 as an inner layer.

In the case of EVOH it is a usual barrier material, also for bottles. Bottles with EVOH as the inner layer only reach drop heights from 1.40 m or less than 1.0 m depending on the outer layer.

Table 1 Table 2

Components

Description Functionalization: type, quantity Density g / cm3 MFR 230 ° C 2.16 kg Tradename Maker

PA MXD6 / MXDI (A1)

MXD6 / MXDI copolyamide of metaxylenediamine, adipic acid and isophthalic acid, with 2 mol% of isophthalic acid with respect to 100 mol% diacid VR 1.63 (measured in 0.5% m-cresol solution by weight at 20 ° C) melting point 234 ° C, amino terminal groups 19 mequiv / kg - - - - EMS-CHEMIE AG, Switzerland

PA MXD6 / MXDI (A2)

MXD6 / MXDI copolyamide of metaxylenediamine, adipic acid and isophthalic acid, with 12 mol% of isophthalic acid, with respect to 100 mol% of diacid VR 1.56 (measured in 0.5% m-cresol solution in weight at 20 ° C) melting point 218 ° C, amino terminal groups 46 mequiv / kg - - - - EMS-CHEMIE AG, Switzerland

PA 610

Polyamide 610 of hexamethylenediamine and sebacic acid VR 1.95 (measured in 0.5% m-cresol solution by weight at 20 ° C) - - - - EMS-CHEMIE AG, Switzerland

PE-HD

High density polyethylene - 0.945 fifteen* Lupolen 4261A LyondellBasell, The Netherlands

E / P-E / B-MAH (B1)

Combination of ethylene / propylene copolymer and ethylene / but-1-eno copolymer in weight ratio 67:33 0.6% maleic acid anhydride by weight 0.875 1.3 Tafmer MC 201 Mitsui Chemicals, Japan

E / P-MAH (B2)

Functionalized olefin copolymer of ethylene and propylene 0.8% maleic acid anhydride by weight 0.870 - Exxelor VA 1810 Exxon Mobil Chemicals, USA

E / B-MAH (B3)

Functionalized olefin copolymer of ethylene and but-1eno 0.8% maleic acid anhydride by weight 0.870 1.8 Tafmer MH 7010 Mitsui Chemicals, Japan

E-MAH (B4)

Copolymer of ethylene olefin and maleic acid anhydride 0.2% by weight maleic acid anhydride 0.924 *** 1.1 ** Admer GT 6 Mitsui Chemicals, Japan

VR relative viscosity * MFR 190 ° C, 21.6 kg ** MFR 190 ºC, 2.16 kg *** tempered 120 ° C, 1 h

Examples

Number

Components

Unity one 2 3 4

PA MXD6 / MXDI (A1)

% in weigh 85 80 - 75

PA MXD6 / MXDI (A2)

% in weigh - - 80 -

E / P-E / B-MAH (B1)

% in weigh fifteen twenty twenty 25

essays

Tensile modulus of elasticity

MPa 2700 2200 2170 1990

Elongation at break

% 35 40 70 35

Impact resistance, Charpy 23 ° C -30 ° C

kJ / m2 330 90 350 100 315 100 315 100

Impact resistance of notched specimen, Charpy 23 ° C -30 ° C

kJ / m2 30 10 75 13 85 15 90 15

Oxygen permeability 0% RH, 23 ° C 50% RH, 23 ° C 85% RH, 23 ° C

cm3 / m2 d bar 11 4 4 11 4 5 12 4 5 14 5 6

Gelbolflex test, 900 cycles

Holes 238 98 94 63

Table 3 (continued)

Examples

Number

Components

Unity 5 6 7 8 9 10 eleven

PA MXD6 / MXDI (A1)

% in weigh 80 80 - 80 80 - 80

PA MXD6 / MXDI (A2)

- - 80 - - 80 -

E / P-MAH (B2)

% in weigh 16 13 13 10 7 7 4

E / B-MAH (B3)

% in weigh 4 7 7 10 13 13 16

essays

Tensile modulus of elasticity

MPa 2200 2240 2200 2190 2130 2210 2210

Elongation at break

% Four. Five 60 35 35 fifty 40 40

Impact resistance, Charpy 23 ° C -30 ° C

kJ / m2 310 100 305 100 315 100 305 100 305 100 320 100 310 100

Impact resistance of notched specimen, Charpy 23 ° C -30 ° C

kJ / m2 25 10 40 11 35 13 65 13 75 14 30 14 65 13

Examples

Number

Components

Unity 5 6 7 8 9 10 eleven

Oxygen permeability 0% RH, 23 ° C 50% RH, 23 ° C 85% RH, 23 ° C

cm3 / m2 d bar 11 4 6 13 5 6 12 4 5 13 5 6 11 5 5 13 4 6 13 4 5

Gelbolflex test, 900 cycles

Holes 138 112 108 115 115 110 138

Table 4

Comparative Examples

Number

Components

Unity 12 13 14

PA MXD6 / MXDI (A1)

% in weigh 95 90 70

E / P-E / B-MAH (B1)

% in weigh 5 10 30

essays

Tensile modulus of elasticity

MPa 3550 3110 1760

Elongation at break

% 8 22 18

Impact resistance, Charpy 23 ° C -30 ° C

kJ / m2 75 60 220 70 285 100

Impact resistance of notched specimen, Charpy 23 ° C -30 ° C

kJ / m2 4 4 8 5 80 16

Oxygen permeability 0% RH, 23 ° C 50% RH, 23 ° C 85% RH, 23 ° C

cm3 / m2 d bar 8 3 3 9 3 4 * * *

Gelbolflex test, 900 cycles

Holes ** ** *

* Too many gel particles, therefore no sheet can be produced ** The sheet is torn

Table 5 Table 6 Table 7

Comparative Examples

Number

Components

Unity fifteen 16

PE-HD

% in weigh fifty 75

PA MXD6 / MXDI (A1)

% in weigh 25 5

E-MAH (B9)

% in weigh 25 twenty

essays

Tensile modulus of elasticity

MPa 1140 825

Elongation at break

% 25 fifteen

Impact resistance, Charpy 23 ° C -30 ° C

kJ / m2 30 19 150 100

Impact resistance of notched specimen, Charpy 23 ° C -30 ° C

kJ / m2 10 10 1 9

Oxygen permeability 0% RH, 23 ° C 50% RH, 23 ° C 85% RH, 23 ° C

cm3 / m2 d bar * * * 2080 2043 2000

Gelbolflex test, 900 cycles

Holes * 1495

* Too many gel particles, therefore no sheet can be produced

Comparative Examples

Number

Components

Unity 17 18 19

PA 610

% in weigh 75 55 fifty

PA MXD6 / MXDI (A1)

% in weigh twenty 30 30

E / P-E / B-MAH (B1)

% in weigh 5 fifteen twenty

essays

Tensile modulus of elasticity

MPa 2450 2165 1985

Elongation at break

% 30 40 65

Impact resistance, Charpy 23 ° C -30 ° C

kJ / m2 360 100 305 100 285 100

Impact resistance of notched specimen, Charpy 23 ° C -30 ° C

kJ / m2 10 7 30 16 55 19

Oxygen permeability 0% RH, 23 ° C 50% RH, 23 ° C 85% RH, 23 ° C

cm3 / m2 d bar 84 53 60 83 50 60 73 41 48

Gelbolflex test, 900 cycles

Holes 432 292 230

Drop test in 3-layer bottles filled and refrigerated, intermediate layer respectively of Admer NF 408 E and N-methylpyrrolidone barrier

Material for outer layer

Material for inner layer Maximum height of resisted fall [m] Weight loss with storage at 40 ° C for 60 days [g / d]

HDPE + regranulated

Example No. 2 2.20 0.017

HDPE + regranulated

PA6, modified to impact 1.80  0.021

HDPE + regranulated

EVOH <1.00 -

HDPE

EVOH 1.40 -

Claims (13)

1. Thermoplastic polyamide molding mass, which contains a) from 71 to 89% by weight of a MXD6 / MXDI copolyamide, the molar part being isophthalic acid, with with respect to all diacids isophthalic acid and adipic acid, 1 to 30 mol%, b) from 11 to 29% by weight of at least one acid modified copolylolefin elastomer or at least one acid-modified combination of several copolyolefin elastomers, c) from 0 to 8% by weight of additives, not containing, in addition to copolymers a) and b), other polymers and / or copolymers and adding components a) to c) to 100% by weight.

2.

 Molding mass according to claim 1, characterized in that the molar part of isophthalic acid in MXD6 / MXDI copolyamide, with respect to all diacids isophthalic acid and adipic acid, is 1 to 20 mol%, preferably of 2 to 15 mol%, particularly preferably 2 to 12 mol%.

3.

 Molding mass according to claim 1, characterized in that the MXD6 / MXDI copolyamide has a maximum of 70 mequiv / kg, preferably 5 to 50 mequiv / kg, particularly preferably 10 to 29 mequiv / kg of amino terminal groups.

Four.

 Molding according to one of the preceding claims, characterized in that the at least one acid-modified copolylolefin elastomer or the at least one acid-modified combination of several copolylolefin elastomers is composed of monomer units that are selected from the compound group by ethylene, propylene and but-1-ene, preferably using the monomers mentioned above in the following molar parts:

d) ethylene: 65-90 mol%, preferably 65-87 mol%, particularly preferably 71-84% in moles, e) propylene: 8-33 mol%, preferably 10-25 mol%, particularly preferably 12-20 % in moles as well as f) but-1-ene: 2-25 mol%, preferably 3-20 mol%, particularly preferably 4-15% in moles, very particularly preferably 4-9 mol% and adding components d) to f) to give 100 mol%

5.

 Molding mass according to one of the preceding claims, characterized in that the degree of modification, that is, the part by weight of the unsaturated carboxylic acids and / or the derivatives of unsaturated carboxylic acids in the copolylolefin elastomer or in the combination of several copolyolphine elastomers, of the acid modified copolyolphine elastomer or of the at least one acid modified combination of several copolyolphine elastomers is 0.3 to 1.5% by weight, preferably 0.4 to 1.2 % by weight, particularly preferably 0.4 to 1.0% by weight, with respect to the acid-modified copolylolefin elastomer or the acid-modified combination of various copolylolefin elastomers.

6.

 Molding according to one of the preceding claims, characterized in that the acid modification of the copolyolefin elastomer or of the combination of several copolyolefin elastomers is carried out by grafting with unsaturated carboxylic acids and / or derivatives of unsaturated carboxylic acids, preferably a carboxylic acid derivative selected from the group consisting of esters of unsaturated carboxylic acids and anhydrides of unsaturated carboxylic acids, particularly with an unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, alpha-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic acid, tetrahydrophthalic acid and / or butenylsuccinic acid.

7.

 Molding according to one of the preceding claims, characterized in that the relative viscosity of MXD6 / MXDI polyamide, measured in 0.5% m-cresol solution by weight at 20 ° C, is 1.40 to 1 , 80, preferably from 1.46 to 1.73, particularly preferably from 1.51 to 1.69, very particularly preferably from 1.53 to 1.66.

8.

 Molding mass according to one of the preceding claims, characterized in that

a) the part by weight of the copolyamide is from 73 to 87% by weight, preferably from 75 to 85% by weight, particularly preferably from 77 to 83% by weight and b) the part by weight of the at least one elastomer of copolylophine modified with acid or of the at least one acid modified combination of several copolyolefin elastomers is from 13 to 27% by weight, preferably from 15 to 25% by weight, particularly preferably from 17 to 23% by weight with respect to the molding mass.

9.

Multilayer container comprising at least one layer that is produced from a molding mass

according to one of the preceding claims.

10.

 Container according to the preceding claim, characterized in that at least the innermost layer is produced from the molding mass.

eleven.

Container according to one of the two preceding claims, characterized in that the at least one

The layer produced from the molding mass has a layer thickness of 15 to 800 µm, preferably 20 to 500 µm, particularly preferably 25 to 250 µm, very particularly preferably 30 to 150 ! m. 12. Container according to one of claims 10 to 12, characterized in that all the layers have a total layer thickness of 500 µm to 10 mm, preferably 600 µm to 6 mm, particularly preferably 700 µm 3 mm A container according to one of claims 10 to 13, characterized in that, charged with a mixture of ethylene glycol-water in the volume ratio of 1: 2 after storage at -20 ° C for 24 to 48 hours, it is not possible they break with a fall from 1.8 m, preferably from 2.0 m, particularly preferably from 2.2 m in height. 14. Use of a container according to one of claims 10 to 14 for agrochemicals (by 15 example, herbicides, pesticides, fungicides, fertilizers), industrial chemicals, precursor products and industrial intermediates, precursor products or cosmetic items (eg solvent, flavor solutions, mascara, nail polish), precursor products or pharmaceutical items and / or precursor products for the food industry.